WO2014146752A1

WO2014146752A1 - Materials for electronic devices

Info

Publication number: WO2014146752A1
Application number: PCT/EP2014/000537
Authority: WO
Inventors: Philipp Stoessel; Amir Hossain Parham; Christof Pflumm; Anja JATSCH
Original assignee: Merck Patent Gmbh
Priority date: 2013-03-22
Filing date: 2014-03-04
Publication date: 2014-09-25
Also published as: EP2976329A1; JP2018184404A; JP6625694B2; JP6926133B2; US10193079B2; EP3375785B1; CN105051014B; CN105051014A; US20160072076A1; EP2976329B1; JP2019131555A; EP3375785A1; KR20150132872A; CN107739352A; JP2016516085A; KR102232333B1

Abstract

The present application relates to a compound of a formula (I) which comprises a benzene group that is substituted with a group selected from carbazole derivatives and bridged amines and with an electron attracting group, wherein the two groups are located in the ortho-position in reslation to one another. The present application further relates to the use of the compound of the formula (I) in an electronic device, and to a method of producing the compound of the formula (I).

Description

Materials for electronic devices

The present application relates to a compound of formula (I) which has a benzene group selected from a group consisting of carbazole derivatives and bridged amines and having a

electron-withdrawing group is substituted, wherein the two groups are in ortho position to each other. The connection can be used in an electronic device. For the purposes of this application, electronic devices are understood as meaning in particular so-called organic electronic devices (organic electronic devices), which are organic

Semiconductor materials as functional materials included. In particular, it is understood to mean, in particular, organic electroluminescent devices (OLEDs) and other electronic devices, which are listed below in the detailed description of the invention.

Generally, the term OLED is an electronic

Device understood that contains at least one organic material and emits light when applying electrical voltage. The exact structure of OLEDs is described inter alia in US 4539507, US Pat.

US 5151629, EP 0676461 and WO 98/27136. In electronic devices, in particular OLEDs, there is great interest in improving the performance data, in particular

Lifetime and efficiency and operating voltage. An important role is played by organic emitter layers, in particular the emitter compounds contained therein.

To solve this technical problem, new materials are continuously being sought which are suitable for use as emitter compounds in emitting layers, in particular in combination with a matrix material. In a system containing two or more materials, a matrix material is understood as the component whose proportion in the mixture is greater. Accordingly, under a dopant in a system containing two or more materials, that becomes

Understood component whose share in the mixture is the smaller.

In the context of the present application, compounds which emit light during operation of the electronic device are regarded as emitter connections of an emitting layer. In emitting layers of OLEDs are generally the

Dotand compound or the dopant compounds the emitting

Compounds, and the matrix compound or the matrix compounds are not light-emitting. However, there may also be exceptions, for example compounds which are present in a small proportion in the mixture of the light-emitting layer, that is to say as dopants according to the above definition, but do not emit, but fulfill other tasks, for example charge transport.

Known in the prior art are compounds containing one or more carbazole groups, for example from WO 2005/039246,

US 2005/0069729, JP 2004/288381, EP 1205527 or WO 2008/086851. The compounds are suitable for use as, inter alia

Matrix materials for emitting layers of OLEDs or as

Compounds for electron-transporting layers of OLEDs.

Furthermore, from WO 2012/143079 compounds are known which have three carbazole groups in 1, 3, 5-position on a benzene.

Other substitutes are then selected, for example

Alkyl groups. The compounds are suitable, inter alia, for

Use in the emitting layer of OLEDs.

Yet again, in H. Uoyama et al., Nature 2012, 492, 234 et seq., Compounds are disclosed which contain a plurality of carbazole groups and a plurality of cyano groups bound to a benzene ring, wherein the

Carbazole groups and the cyano groups in a defined arrangement to stand by each other. There are basically at least two

Carbazole groups arranged para to the benzene ring. The

Compounds are used in the emitting layer of OLEDs.

Despite these results, there remains a need for new compounds that are suitable for use in electronic devices, particularly for use in emissive layers of OLEDs.

It has now surprisingly been found that compounds which have at least one carbazole derivative bonded to a benzene ring and in the ortho position to at least one electron-withdrawing group, wherein the substituents on the benzene ring in a defined arrangement, as defined in the formula (I) below, to each other are very well suited for use in electronic devices. In particular, they are eminently suitable for use as emitter compounds in emitting layers.

Surprisingly, OLEDs containing the compounds have a very good power efficiency and a very long service life.

Furthermore, they preferably have a low operating voltage.

Again, when used as an emitter compound, they can potentially cover the entire color spectrum of the emission.

The subject of the present application is thus a compound of the formula (I)

Formula (I) or a compound containing exactly two or three units according to the formula (I), which has a single bond or a group L

are linked together, where:

L is any divalent or trivalent organic group;

A is a group of the formula (A)

Formula (A),

which is bound via the dashed bond;

Ar ¹ is the same or different at each occurrence and is an aromatic or heteroaromatic ring system having from 5 to 30 aromatic ring atoms which may be substituted by one or more R radicals;

Y is the same or different at each occurrence

Single bond, BR ¹ , C (R ¹ ) ₂ , Si (R) ₂ , NR ¹ , PR ¹ , P (= O) R ¹ , O, S, S = O or S (= O) ₂ ;

B is the same or different selected on each occurrence from a group of formula (A), H, D, a straight-chain Aikylgruppe having 1 to 20 C-atoms or a branched or cyclic Aikylgruppe having 3 to 20 C-atoms, each with a or a plurality of radicals R ¹ may be substituted, wherein one or more CH ₂ groups in the abovementioned groups by - R ¹ C = CR ¹ -, -CEC-, Si (R ¹ ) ₂ , C = 0, C = NR ¹ , -C (= O) O-, -C (= O) NR ¹ -, NR ¹ , P (= O) (R ¹ ), -O-, -S-, SO or SO ₂ may be replaced, and an aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms, each of which may be substituted by one or more radicals R ¹ ; is the same or different at each occurrence F, CF ₃ , C (= O) R ¹ , CN, P (= O) (R ¹ ) ₂ , S (= 0) R ¹ , S (= 0) ₂ R 1 straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, each of which may be substituted by one or more radicals R ¹ , and wherein one or more CH ₂ groups in the above-mentioned groups by -RC = CR ¹ -, -CEC-, Si (R) _2t C = O, C = NR ¹ , -C (= O) O-, -C (= O) NR ¹ -, NR ¹ , P ( = O) (R ¹ ), -O-, -S-, SO or SO ₂ may be replaced, or an aromatic ring system having 6 to 30 aromatic ring atoms, which may be substituted by one or more radicals R ¹ , or a heteroaromatic Ring system having 5 to 30 aromatic ring atoms, which is not bound via a ring nitrogen atom, and which may be substituted with one or more radicals R ¹ , wherein radicals R ^A may be linked to radicals R ¹ and form a ring; is selected from H, D and the radicals listed above for R ^A , where radicals R ^B can be linked to radicals R ¹ and can form a ring; is identical or different at each occurrence H, D, F, C (= O) R ² , CN, Si (R ² ) ₃ , N (R ² ) ₂ , P (= O) (R ² ) ₂₎ OR ² , S (= O) R ² , S (= O) ₂ R ² , a straight-chain alkyl or alkoxy group having 1 to 20 C atoms or a branched or cyclic alkyl or alkoxy group having 3 to 20 C atoms, wherein the above groups can each be substituted by one or more radicals R ² and wherein one or more CH ₂ groups in the abovementioned groups by -R ² C = CR ² -, -CsC-, Si (R ² ) ₂ , C = O, C = NR ² ,

-C (= O) O-, -C (= O) NR ² - NR ² , P (= O) (R ² ), -O-, -S-, SO or SO ₂ may be replaced, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, each substituted by one or more radicals R ² can, wherein two or more radicals R ^{1 may} be linked together and form a ring;

R ² is the same or different H, D, F or an aliphatic, aromatic or heteroaromatic organic radical having 1 to 20 C-atoms, in which also one or more at each occurrence

H atoms can be replaced by D or F; two or more substituents R ^{2 may} be linked together and form a ring; with the proviso that at least one R ^{A is} selected from F, CF ₃ , CF ₂ H, CFH ₂ , C (= O) R ¹ , CN, P (= O) (R) _{2 L} S (= O) R ¹ , S (= O) ₂ R ¹ or a group E, which is an aryl or heteroaryl group having 6 to 18 aromatic ring atoms which may be substituted by one or more radicals R ¹ , and which as constituents of the aromatic ring one or contains several groups V, wherein the groups V are the same or different at each occurrence of = N-, = C (F) -, = C (CN) - and = C (CF ₃ ) -.

Heteroaromatic ring systems which are bonded via a ring nitrogen atom, in particular derivatives of

Carbazoles, indenocarbazoles, indolocarbazoles, pyrroles and imidazoles bound via their corresponding nitrogen atom with free valence.

An aryl group in the sense of this invention contains 6 to 60 aromatic ring atoms; For the purposes of this invention, a heteroaryl group contains 5 to 60 aromatic ring atoms, at least one of which represents a heteroatom. The heteroatoms are preferably selected from N, O and S. This is the basic definition. If other preferences are given in the description of the present invention, for example with respect to the number of aromatic ring atoms or the heteroatoms contained, these apply.

In this case, an aryl group or heteroaryl group is either a simple aromatic cycle, ie benzene, or a simpler one

heteroaromatic cycle, for example pyridine, pyrimidine or Thiophene, or a condensed (fused) aromatic or

heteroaromatic polycycle, for example, naphthalene, phenanthrene, quinoline or carbazole understood. A condensed (anneliierter) aromatic or heteroaromatic polycycle consists in the context of the present application of two or more condensed simple aromatic or heteroaromatic cycles.

Under an aryl or heteroaryl group, which may be substituted in each case with the abovementioned radicals and which may be linked via any position on the aromatic or heteroaromatic, are

especially groups understood which are derived from benzene, naphthalene, anthracene, phenanthrene, pyrene, dihydropyrene, chrysene, perylene, fluoranthene, benzanthracene, benzphenanthrene, tetracene, pentacene, benzopyrene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, Dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine,

Phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthimidazole, phenanthrimidazole, pyrimididazole, pyrazine imidazole, quinoxaline imidazole, oxazole, Benzoxazole, naphthoxazole, antifiroxazole, phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole,

Pyridazine, benzopyridazine, pyrimidine, benzpyrimidine, quinoxaline, pyrazine, phenazine, naphthyridine, azacarbazole, benzocarboline, phenanthroline, 1, 2,3-triazole, 1, 2,4-triazole, benzotriazole, 1, 2,3-oxadiazole, 1, 2,4-oxadiazole, 1, 2,5-oxadiazole, 1, 3,4-oxadiazole, 1,2,3-thiadiazole, 1, 2,4-thiadiazole, 1,2,5-thiadiazole, 1, 3, 4-thiadiazole, 1, 3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1, 2,3,4-tetrazine, 1, 2,3,5-tetrazine, purine,

Pteridine, indolizine and benzothiadiazole.

An aromatic ring system in the sense of this invention contains 6 to 60 carbon atoms in the ring system. A heteroaromatic ring system in the context of this invention contains 5 to 60 aromatic ring atoms, at least one of which represents a heteroatom. The heteroatoms are preferably selected from N, O and / or S. An aromatic or heteroaromatic ring system in the context of this invention is to be understood as meaning a system which does not necessarily contain only aryl or aryl Heteroaryl contains but in which also several aryl or heteroaryl groups by a non-aromatic unit (preferably less than 10% of the atoms other than H), such as. For example, an sp ³ - hybridized C, Sh N or O atom, an sp ² -hybridized C or N atom or a sp-hybridized carbon atom can be connected. For example, systems such as 9,9'-spirobifluorene, 9,9'-diarylfluorene, triarylamine, diaryl ethers, stilbene, etc. are to be understood as aromatic ring systems in the context of this invention, and also systems in which two or more aryl groups, for example by a linear or cyclic alkyl, alkenyl or alkynyl group or linked by a silyl group. Furthermore, systems in which two or more aryl or heteroaryl groups are linked together via single bonds are understood as aromatic or heteroaromatic ring systems in the context of this invention, such as systems such as biphenyl, terphenyl or diphenyltriazine.

An aromatic or heteroaromatic ring system having 5-60 aromatic ring atoms, which may be substituted in each case by radicals as defined above and which may be linked via any positions on the aromatic or heteroaromatic compounds, is understood in particular to mean groups derived from benzene, naphthalene .

Anthracene, benzanthracene, phenanthrene, benzphenanthrene, pyrene, chrysene, perylene, fluoranthene, naphthacene, pentacene, benzpyrene, biphenyl, biphenylene, terphenyl, terphenylene, quaterphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene, Truxen , Isotruxene, spirotruxene, spiroisotruxene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene,

Benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole,

Isoindole, carbazole, indolocarbazole, indenocarbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, Imidazole, benzimidazole, naphthimidazole, phenanthrimidazole, pyrimididazole, pyrazine-imidazole, quinoxalinimidazole, oxazole, benzoxazole, naphthoxazole,

Anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzpyrimidine, quinoxaline, 1,5-diazaanthracene, 2,7-diazapyrene, 2,3-diazapyrene, 1, 6-diazapyrene, 1, 8- Diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazaperylene, pyrazine, phenazine, phenoxazine, phenothiazine, fluorubin, naphthyridine, azacarbazole, benzo-carboline, phenanthroline, 1, 2,3-triazole, 1,2, 4-triazole, benzotriazole, 1, 2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1, 3,4-oxadiazole, 1,2,3-thiadiazole, 1,2, 4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1, 2,4-triazine, 1,2,3-triazine, tetrazof, 1,2, 4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine and benzothiadiazole, or combinations of these groups.

In the context of the present invention, a straight-chain alkyl group having 1 to 40 C atoms or a branched or cyclic alkyl group having 3 to 40 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms, in which also individual H atoms or CH ₂ groups may be substituted by the groups mentioned above in the definition of the radicals, preferably the radicals methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t Butyl, 2-methylbutyl, n-pentyl, s-pentyl, cyclopentyl, neo-pentyl, n-hexyl, cyclohexyl, neo-hexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl , 2,2,2-trifluoroethyl, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl,

Cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl or octynyl understood. Among an alkoxy or thioalkyl group having 1 to 40 carbon atoms, methoxy, trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, s Pentoxy, 2-methylbutoxy, n-hexoxy, cyclohexyloxy, n-heptoxy, cycloheptyloxy, n-octyloxy,

Cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy, 2,2,2-trifluoroethoxy, methylthio, ethylthio, n-propylthio, i-propylthio, n-butylthio, i-butylthio, s-butylthio, t-butylthio, n-pentylthio, s Pentylthio, n-hexylthio, cyclohexylthio, n-heptylthio, cycloheptylthio, n-octylthio, cyclooctylthio, 2-ethylhexylthio, trifluoromethylthio, pentafluoroethylthio, 2,2,2-trifluoroethylthio, ethenylthio, propenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthio, cyclohexenylthio, Heptenylthio, cycloheptenylthio, octenylthio,

Cyclooctenylthio, ethynylthio, propynylthio, butynylthio, pentynylthio,

Hexinylthio, heptynylthio or octynylthio understood. In the context of the present application, it is to be understood, inter alia, that the two radicals are linked together by a chemical bond, under the formulation that two or more radicals can form a ring with one another. This is illustrated by the following scheme:

Furthermore, it should also be understood by the above-mentioned formulation that in the event that one of the two radicals

Is hydrogen, the second moiety bonding to the position to which the hydrogen atom was attached to form a ring. This will be illustrated by the following scheme:

The group L is preferably a divalent group selected from

Alkylene groups having 1 to 20 carbon atoms, in which one or more CH ₂ - groups by Si (R ¹ ) _2> 0, S, C = 0, C = NR ¹ , C = 0-0, C = 0-NR ¹ , NR ¹ , P (= O) (R ¹ ), SO or SO ₂ may be replaced and may be substituted by one or more radicals R, or aromatic or heteroaromatic ring systems having 5 to 30 aromatic ring atoms, each by a or a plurality of radicals R ¹ may be substituted, or a trivalent group selected from aromatic or heteroaromatic ring systems having 5 to 30 aromatic ring atoms, each of which may be substituted by one or more radicals R ¹ .

Formula (A) preferably corresponds to one of the following formulas (A-1) to (A-22) attached via the dotted bond

Formula (A-7)

Formula (A-15) Formula (A-16)

Formula (A-17) Formula (A-18)

Formula (A-19) Formula (A-20)

Formula (A-2) Formula (A-22) where X is the same or different CR ¹ or N at each occurrence;

U is equal to BR ¹ , C (R ¹ ) ₂ , Si (R 1 \ UD I

T) 2, NR ¹ , O or S; and

R ¹ is defined as above.

Preferred among the formulas (A-1) to (A-22) are the formulas (A-1), (A-4), (A-14) and (A-17).

When U is a group C (R ¹ ) ₂ or Si (R ¹ ) ₂ , it is preferred that the two groups R of the group are linked together and one Form ring. Preferably, a five- or six-membered ring is formed. Particularly preferred is a spiro-bifluorene group.

It is preferable for the above formulas that X is CR ¹ . It is further preferable for the above formulas that not more than three groups X per ring are equal to N. Further, it is preferable that not more than two adjacent groups X in a ring are equal to N. More preferably, exactly one group X per ring is N, or no group X per ring is N.

Preferably, the group U in the above formulas is C (R ¹ ) 2 or NR ¹ , more preferably C (R ¹ ) ₂ .

Particularly preferred are combinations of the above

preferred embodiments with each other.

Preferably, each occurrence of Ar ^{1 is,} identically or differently, an aromatic ring system having from 6 to 20 aromatic ring atoms which may be substituted by one or more R radicals, and more preferably phenyl, pyridyl, naphthyl, fluorenyl or carbazolyl, each containing one or more can be substituted by several radicals R ¹ .

Preferably, the group Y is the same or different at each instance and is a single bond, C (R ¹ ) ₂ , NR ¹ , O or S, more preferably a single bond.

For group B, it is preferred according to the invention that it is the same or different selected on each occurrence from a group of formula (A), H, a straight-chain alkyl group having 1 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 C atoms, each of which may be substituted by one or more radicals R ¹ , or an aryl group having 6 to 14 aromatic ring atoms, each of which may be substituted by one or more R radicals. When the group B is selected from a group of the formula (A), it is preferable that it is selected from groups of the formulas (A-1) to (A-22). With particular preference, the group B is the same or different at each occurrence and is a group of the formula (A) or H. More preferably, the group B is a group of the formula (A). When the group B is a group of the formula (A), it is preferable that it is selected from groups of the formulas (A-1) to (A-22).

It follows from the definition of R ^A and R ^B that these may not be bound via the nitrogen carbazole or carbazole derivative. Of the radical R ^A, it is preferable in the invention that it is the same or different selected at each occurrence from F, CF ₃₎ CN, a straight-chain alkyl group having 1 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 C Atoms, each of which may be substituted by one or more radicals R ¹ , or an aryl or heteroaryl group having 6 to 14 aromatic ring atoms, which may be substituted by one or more radicals R, wherein the

Heteroaryl group is not bound via a nitrogen atom, provided that at least one radical R ^{A is} selected from F, CF ₃ , CN, or a group E, which is an aryl or heteroaryl group having 6 to 14 aromatic ring atoms, with a or a plurality of radicals R ¹ and which contains, as constituents of the aromatic ring, one or more groups V, the groups V on each occurrence being identically or differently selected from = N-, = C (F) -, = C ( CN) - and = C (CF ₃ ) -.

Particularly preferably, both radicals R ^{A are the} same or different selected from F, CF ₃ , CN, and a group E which is an aryl or heteroaryl group having 6 to 14 aromatic ring atoms which may be substituted by one or more radicals R ¹ , and as components of the

aromatic ring contains one or more groups V, wherein the

Groups V are chosen the same or different at each occurrence from = N-, = C (F) -, = C (CN) - and = C (CF ₃ ) -. The heteroaryl group is not bound via a nitrogen atom. It is preferred that at least two groups V are present in the groups E, more preferably two, three, four or five.

Group E is preferably a group of formula (E-1) to (E-9) attached via the dotted bond

Formula (E-1) Formula (E-2) Formula (E-3)

Formula (E-4) Formula (E-5) Formula (E-6)

Formula (E-7) Formula (E-8) Formula (E-9) wherein: at each occurrence, the same or different is CR ¹ or V, wherein at least one group W is V; and wherein V and R ^{1 are} defined as above. Preferred among the groups of the formulas (E-1) to (E-9) is the group of the formula (E-1).

In the groups of the formulas (E-1) to (E-9), at least two groups W are preferably equal to V, more preferably exactly two, three, four or five.

Furthermore, it is preferable that not more than two groups V, which are equal to = N-, are present side by side in a ring. Further preferably, not more than three groups V, which are equal to = N-, exist in a ring.

Particularly preferred embodiments of the groups E correspond to the following formulas (E-1-1) to (E-1-89)

(E-1-1) (E-1-2) (E-1-3) (E-1-4)

(E-1-6) (E-1-7) (E-1-8) (E-9) (E-1-10)

(E-12) (E-1-13) (E-1-14)

(E-1-16) (E-1-17) (E-1-19) (E-1-20)

N

(E-1-21) (E-1-22) (E-1-23) (E-1-24) (E- -25)

(E-1-26) (E-1-27) (E-28) (E-1-29) (E-1-30)

(E-1-36) (E-1-37) (E-1-38) (E-1-39) (E-1-40)

(E-1-41) 42) (E-1-43) (E-1-44)

(E-1-45) (E-1-46) (E-1-47) (E-1-8) (E-1-49)

(E-1-50) (E-1-52) (E-1-53) (E-1-54)

(E-1-55) (E-1-56) (E-1-57) (E-1-58) (E-1-59)

(E-1-60) (E-1-61) (E-1-62) (E-1-63) (E-1-64)

(E-1-65) (E-1-66) (E-1-67) (E-1-68) (E-1-69)

(E-1-71) (E-1-72) (E-1-73) (E-1-74)

(E-1-75) (E-1-76) (E-1-77) (E-1-78) (E-79)

(E-1-80) (E-1-81) (E-1-82) (E-1-83) (E-1-84)

Preferably, R ^{B is the} same or different at each occurrence selected from H, F, CF ₃ , CN, a straight-chain alkyl group having 1 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms, each with one or a plurality of R may be substituted, and an aryl or heteroaryl group having 6 to 14 aromatic ring atoms which may be substituted with one or more radicals R ¹ , wherein the heteroaryl group is not bound via a nitrogen atom. More preferably, R ^{B is the} same or different at each instance selected from H, F, CF ₃ , CN, and a group E as defined above. The radical R ¹ in each occurrence is identical or different and is H, D, F, CN, Si (R ² ) 3, N (R ² ) ₂ , a straight-chain alkyl or alkoxy group having 1 to 10 C atoms or a branched one or cyclic alkyl or alkoxy group having 3 to 10 C atoms, where the abovementioned groups can each be substituted by one or more radicals R ² and where in the abovementioned groups one or more CH ₂ groups is replaced by -R ² C = CR ² , -CEC, Si (R ² ) ₂ , C = O, C = NR ² , -C (= O) O-, -C (= O) NR ² -, NR ² , P (= O ) (R ² ), -O-, -S-, SO or SO ₂ may be replaced, or a

aromatic or heteroaromatic ring system with 5 to 20

aromatic ring atoms, which may be substituted in each case with one or more radicals R ² , wherein two or more radicals R ^{1 may} be linked together and form a ring.

Preferred embodiments of the compounds of the formula (I) correspond to the formulas (1-1) to (I-3)

Formula (1-1) Formula (I-2) Formula (I-3), wherein to the free positions on the benzene ring in formula (I-2) optionally H, D, alkyl groups having 1 to 10 carbon atoms or aromatic or

heteroaromatic ring systems may be bonded with 6 to 30 aromatic ring atoms, each of which may be substituted by one or more radicals R ¹ , and

wherein the groups A, R ^A and R ^{B are} as defined above, and the proviso is that at least one radical R ^{A is} selected from F, CF ₃ , C (= O) R ¹ , CN, P (= O) ( R ¹ ) ₂ , S (= O) R ¹ , S (= O) ₂ R ¹ or a group E which is an aryl or heteroaryl group having 6 to 18 aromatic ring atoms which are substituted by one or more radicals R ¹ can, and contains as constituents of the aromatic ring one or more groups V, wherein the Groups V are chosen the same or different at each occurrence from = N-, = C (F) -, = C (CN) - and = C (CF ₃ ) -. Preferably, the proviso applies to both radicals R ^A

Further preferred is the combination of the preferred

Embodiments of in particular A, B and R ^A and R ^B having the formulas (1-1) to (I-3).

More preferably, in the formulas (1-1) to (I-3), the group A is one of the formulas (A-1) to (A-22) as defined above.

Particularly preferred embodiments of the compounds of

Formula (I) are the compounds of the formula (1-1-a) to (1-1-f)

Formula (I-1-a)

Formula (1-1-e)

Formula (1-1-f), where:

X is defined as above and is preferably equal to CR ¹ ; R ^A and R ^B are defined as above; and with the proviso that at least one radical R ^{A is} selected from F, CF ₃₎ C (= ^O ) R ¹ , CM, P (= O) (R ¹ ) _2> S (= 0) R ¹ , S (= 0) ₂ R ¹ or a group E which has an aryl or heteroaryl group with 6 to 18 aromatic

Is a ring atom which may be substituted by one or more radicals R and which contains, as constituents of the aromatic ring, one or more groups V, the groups V being the same or different each occurrence, from = N-, = C (F) -, = C (CN) - and = C (CF ₃ ) -, and wherein the proviso is preferably for both radicals R ^A.

Preferably, R ^A and R ^B on each occurrence are the same or different, F, CF ₃ , CN, or a group E as defined above. Particularly preferred embodiments of the compounds of the formula (I) are the compounds of the formulas (I-2-a) to (I-2-f)

Formula (1-2-c) Formula (1-2-d)

Formula (I-2-e) Formula (I-2-f) wherein the free positions on the benzene ring in formulas (1-2-1) to (l-2-f) optionally H, D, alkyl groups having 1 to 10 carbon atoms or aromatic or heteroaromatic ring systems having 6 to 30 aromatic

Ring atoms may be bonded, which may be substituted in each case with one or more radicals R ¹ , and wherein

X is defined as above and is preferably equal to CR ¹ ; R ^A and R ^B are defined as above; and with the proviso that at least one radical R ^{A is} selected from F, CF ₃ , C (= ^O ) R ¹ , CN, P (= O) (R ¹ ) ₂₎ S (= 0) R ¹ , S (= 0) ₂ R ¹ or a group E which has an aryl or heteroaryl group with 6 to 18 aromatic

Is a ring atom which may be substituted by one or more radicals R and which contains, as constituents of the aromatic ring, one or more groups V, the groups V on each occurrence being identically or differently selected from -N-, = C (F) -, = C (CN) - and = C (CF ₃ ) -, and wherein the proviso is preferably for both radicals R ^A.

Preferably, R ^A and R ^B on each occurrence are the same or different, F, CF ₃ , CN, or a group E as defined above.

Particularly preferred embodiments of the compounds of

Formula (I) are the compounds of the formula (I-3-a) to (I-3-f)

Formula (I-3-a) Formula (I-3-b)

Formula (I-3-e) Formula (I-3-f) wherein:

X is defined as above and is preferably equal to CR ¹ ; R ^A is defined as above; and with the proviso that at least one radical R ^{A is} selected from F, CF _3> C (= 0) R \ CN, P (= 0) (R) ₂ , S (= 0) R, S (= 0 ) ₂ R or a group E which has an aryl or heteroaryl group with 6 to 18 aromatic

Ring atoms, which may be substituted by one or more radicals R ¹ , and which contains as constituents of the aromatic ring one or more groups V, wherein the groups V in each occurrence are the same or different selected from = N-, = C (F ) -, = C (CN) - and = C (CF ₃ ) -, and where the proviso is preferably for both radicals R ^A. Preferably, R ^{A is the} same or different at each occurrence F, CF ₃ , CN, or a group E as defined above.

Examples of compounds according to the present invention are shown below:

30

35

30

35

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

30

35





25

30

35















The compounds according to formula (I) can be prepared using known organic chemical synthesis steps, for example bromination, boronation, nucleophilic aromatic

Substitution and transition-metal-catalyzed coupling reaction, for example Buchwald coupling.

Scheme 1 shows an exemplary process for the preparation of

Compounds according to formula (I) starting from a cyano-substituted compound (in many cases commercially available) carrying one or more fluorine substituents. In this case, one or more carbazole derivatives are introduced by nucleophilic aromatic substitution. The process can be carried out stepwise so that first one carbazole derivative, and then another, another

Carbazole derivative, can be introduced (see bottom line). Instead of CN, other electron-withdrawing groups can be used. The compounds shown can be optionally further substituted, according to the substituents defined in claim 1. This applies to all the following schemes which explain synthesis methods. Scheme 1

-H = optionally substituted carbazole derivative

= Halogen, preferably F

Furthermore, carbazole derivatives can also be introduced by Buchwald coupling in the compounds of the invention. This is exemplified in Scheme 2 for a compound bearing a CF ₃ group. However, there could be other groups, such as CN or F or electron-deficient heteroaromatic be present instead of CF _3.

Scheme 2

-H = optionally substituted carbazole derivative

= Halogen, preferably Cl, Br

An alternative to Scheme 2 procedure for the introduction of a

Carbazole derivative shows Scheme 3. It is based on a nitro-benzene derivative, which is converted to an amino-benzene derivative, which then undergoes a double Buchwald coupling with a suitable halogen-substituted biaryl. Instead of the C ₆ F ₅ group shown Other groups, for example F, CF ₃ or CN, may also be present.

Scheme 3

-H = optionally substituted carbazole derivative

= Halogen, preferably Cl, Br

Compounds in which a carbazole derivative is adjacent to an electron-withdrawing heteroaromatic can be prepared as shown in Scheme 4 below. For this purpose, it is assumed that a carbazole-phenyl derivative, which is a

Has halogen substituent or another suitable leaving group. This compound is converted into a boronic acid, with which then in a second step a Suzuki coupling with a

electron-deficient aromatics is carried out. By two-fold Suzuki coupling compounds can be prepared, the two

carry different heteroaryl substituents.

Scheme 4

Cbz-H = optionally substituted carbazole derivative

R = any organic radical

Ar * = electron-poor heteroaromatic, preferably triazine or pyrimidine Hal = halogen, preferably Cl The synthetic methods shown above are indications for the

A person skilled in the art, how compounds according to the invention can be prepared over the entire breadth of the claims of the present application. The expert will be the concrete for more detailed explanation

Use embodiments that are included in the application. He continues to draw his general expertise on organic chemical synthesis methods and uses commercially available compounds as starting materials to produce compounds of the invention, the synthesis of which is not explicitly described herein. Furthermore, within the scope of his general knowledge, he may modify the methods described herein, if this provides practical advantages.

The subject of the present invention is summarized

A process for the preparation of a compound of formula (I), characterized in that at least one carbazole derivative is introduced by nucleophilic aromatic substitution or Buchwald coupling, or in that at least one electron-deficient heteroaryl group is introduced by Suzuki coupling. Preference is given to the concrete synthesis methods given above,

The compounds according to the invention, in particular compounds which are substituted by reactive leaving groups, such as bromine, iodine, chlorine, boronic acid or boronic acid esters, can be used as monomers for

Generation of corresponding oligomers find use. Suitable reactive leaving groups are, for example, bromine, iodine, chlorine, boronic acids, boronic esters, amines, alkenyl or alkynyl groups with terminal CC double bond or CC triple bond, oxiranes, oxetanes, groups which carry out a cycloaddition, for example 1, 3 dipolar cycloaddition, such as dienes or azides,

Carboxylic acid derivatives, alcohols and silanes.

Another object of the invention are therefore oligomers containing one or more compounds of formula (I), wherein the bond (s) to the oligomer at any, in formula (I) with R ¹ or R ² substituted

Positions can be located. Depending on the connection of the connection According to formula (I), the compound is part of a side chain of the oligomer or part of the main chain. An oligomer in the context of this invention is understood as meaning a compound which comprises at least four monomer units and at most nine

Monomer units is constructed. The oligomers of the invention may be conjugated, partially conjugated or non-conjugated. The

oligomers of the invention may be linear or branched. In the linearly linked structures, the units of the formula (I) may be directly linked together or may have a divalent group, for example via a substituted or unsubstituted alkylene group, via a heteroatom or via a bivalent aromatic or

heteroaromatic group linked together. In branched structures, for example, three or more units of the formula (I) may have a trivalent or higher valent group, for example a trivalent or higher valent aromatic or higher valent group

heteroaromatic group linked to a branched oligomer.

For the repeating units according to formula (I) in oligomers, the same preferences apply as described above for compounds according to formula (I).

The oligomers according to the invention can be prepared by oligomerization of one or more types of monomer, of which at least one monomer in the oligomer leads to repeat units of the formula (I). To prepare the oligomers, the monomers according to the invention are homopolymerized, for example, or copolymerized with other monomers. Suitable oligomerization reactions are known in the art and described in the literature.

However, the oligomers can also be prepared by stepwise organic synthesis.

The oligomers according to the invention have advantageous properties, in particular high lifetimes, high efficiencies and good

Color coordinates. The compound according to formula (I) is suitable for use in an electronic device, in particular an organic electroluminescent device (OLED). Depending on the substitution, the compound of the formula (I) can be used in different functions and layers. Preference is given to the use in an emitting layer, particularly preferably as an emitting compound in an emitting layer.

Another object of the invention is therefore the use of a compound according to formula (I) in an electronic device. In this case, the electronic device is preferably selected from the group consisting of organic integrated circuits (OICs), organic field effect transistors (OFETs), organic thin film transistors (OTFTs), organic light emitting transistors (OLETs),

organic solar cells (OSCs), organic optical detectors, organic photoreceptors, organic field quench devices

(OFQDs), organic light-emitting electrochemical cells

(OLECs), organic laser diodes (O-lasers) and more preferably organic electroluminescent devices (OLEDs).

The invention furthermore relates to an electronic device containing at least one compound of the formula (I). In this case, the electronic device is preferably selected from the abovementioned devices.

Particularly preferred is an organic electroluminescent device comprising anode, cathode and at least one emitting layer, characterized in that at least one organic layer is contained in the device, which contains at least one compound according to formula (I). Preference is given to an organic electroluminescent device comprising anode, cathode and at least one emitting layer, characterized in that at least one organic layer in the device, selected from emitting layers, contains at least one compound according to formula (I). In addition to the cathode, anode and emitting layer, the electronic device may contain further layers. These are, for example, selected from in each case one or more hole injection layers,

Hole transport layers, hole blocking layers, electron transport layers, electron injection layers, electron blocking layers, exciton blocking layers, interlayers,

Charge Generation Layers (IDMC 2003, Taiwan, Session 21 OLED (5), T. Matsumoto, T. Nakada, J. Endo, K. Mori, N. Kawamura, A. Yokoi, J. Kido, Multiphoton Organic EL Device Having Charge Generation ί3γβή and / or organic or inorganic p / n transitions It should be noted, however, that not necessarily each of these layers must be present and the choice of layers always depends on the compounds used and in particular on the fact whether it is a fluorescent or phosphorescent electroluminescent device.

The sequence of the layers of the electronic device is preferably as follows:

-Anode-

Hole injection layer hole transport layer

-optionally further hole transport layers-

-emitting layer-

-Elektronentransportschicht-

-Electron Injection Layer -Cathode-.

Not all of the layers mentioned must be present, and additional layers may additionally be present.

The person skilled in the art from the literature suitable compounds are known, which he can use in the appropriate layers.

Preferred as the cathode of the electronic device are low work function metals, metal alloys or multilayer structures of various metals, such as alkaline earth metals, alkali metals, main group metals or lanthanides (eg Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Also suitable are alloys of an alkali or alkaline earth metal and silver, for example an alloy of magnesium and silver. In multilayer structures, it is also possible, in addition to the metals mentioned, to use further metals which have a relatively high work function, such as, for example, As Ag or Al, which then usually combinations of metals, such as Ca / Ag, Mg / Ag or Ba / Ag are used. It may also be preferred to introduce between a metallic cathode and the organic semiconductor a thin intermediate layer of a material with a high dielectric constant. For this example, come alkali metal or

Alkaline earth metal fluorides, but also the corresponding oxides or

Carbonates in question (eg LiF, Li ₂ O, BaF ₂ , MgO, NaF, CsF, Cs ₂ CO ₃ , etc.). Furthermore, lithium quinolinate (LiQ) can be used for this purpose.

As the anode, high workfunction materials are preferred. Preferably, the anode has a work function greater than 4.5 eV. Vacuum up. On the one hand, metals with a high redox potential, such as Ag, Pt or Au, are suitable for this purpose. On the other hand, metal / metal oxide electrodes (eg Al / Ni / NiO _x , Al / PtO _x ) may also be preferred. For some applications, at least one of the electrodes must be transparent or

be partially transparent to either the irradiation of the organic

Material (organic solar cell) or the extraction of light (OLED, O-LASER) to allow. Preferred anode materials here are conductive mixed metal oxides. Particularly preferred are indium tin oxide (ITO) or indium zinc oxide (IZO). Preference is furthermore given to conductive, doped organic materials, in particular conductive doped polymers. Furthermore, the anode can also consist of several layers, for example of an inner layer of ITO and an outer layer of a metal oxide, preferably tungsten oxide,

Molybdenum oxide or vanadium oxide.

When the compound of the formula (I) is used as the emitting compound in an emitting layer, it is preferable that as a further component in the layer there is a matrix compound as defined above. In this case, the matrix compounds as the

Be used for this purpose, For example, 4,4 '- (biscarbazol-9-yl) biphenyl (CBP), or 2,8-bis (diphenylphosphoryl) dibenzo [b, d] thiophene (PPT).

Furthermore, in the case of use as the emitting compound, it is preferable that the compound is contained in a proportion between 0.1 and 0.1

50.0 vol .-%, more preferably between 0.5 and 20.0 vol .-% and very particularly preferably between 0.5 and 8.0 vol .-% in the emitting layer is present.

For the production of the electronic device, methods suitable for the person skilled in the art are known. In particular, the device is after

Application of the layers according to (depending on the application) structured, contacted and finally sealed to exclude damaging effects of water and air. Electronic devices containing one or more compounds according to formula (I) can be used inter alia in displays, as light sources in illumination applications and as light sources in medical or cosmetic applications (for example light therapy).

Exemplary embodiments A) Synthesis examples:

Unless stated otherwise, the following syntheses are carried out under an inert gas atmosphere in dried solvents. The metal complexes are additionally handled in the absence of light or under yellow light. The solvents and reagents can be obtained, for example, from Sigma-ALDRICH or ABCR. I) Synthesis of compounds of the invention:

Example S1: 1,3,5-tris-cyano-2A6-tris (N-carbazolyl) benzene

Option A:

A well-stirred suspension of 16.0 g (400 mmol) of sodium hydride, 60 wt .-% dispersion in mineral oil, in 500 ml of THF is under ice cooling at about + 10 ° C in portions with 66.9 g (400 mmol) of carbazole [51555-21 -6] - Beware of hydrogen evolution! Foam! After completion of the addition, the mixture is 30 min. stirred and then added portionwise with ice cooling so with 20.7 g (100 mmol) of 1,3,5-tricyano-2,4,6-trifluorobenzene [363897-9] that the temperature does not exceed + 20 ° C. After completion of the addition, the mixture is stirred for 2 h at + 10 ° C, then removed the cooling bath, allowed to warm to 20 - 25 ° C, stirred for 2 h and then heated for 12 h at 40 ° C. After cooling to

Room temperature, the reaction is terminated by dropwise addition of 30 ml of MeOH and the reaction mixture concentrated in vacuo almost to dryness. The residue is stirred hot twice with 600 ml of a mixture of 400 ml of methanol and 200 ml of water and then once with 500 ml of methanol. Purification is carried out by recrystallizing three times from dioxane (about 5 ml / g) followed by five recrystallizations from DMF (about 2.5 ml / g) and two times fractionated sublimation (p about 1 × 10 ^-5 mbar, T about 310-320 ° C). Yield: 23.6 g (36.3 mmol) 36%. Purity: 99.9% n. HPLC.

Variant B:

Procedure analogous to variant A, but the carbazole is initially charged in THF and then added dropwise with 160 ml (400 mmol) of n-Buü, 2.5 molar in n-hexane. Yield: 19.0 g (29.3 mmol) 29%. Purity: 99.9% n. HPLC. Variant C:

A well-stirred suspension of 66.9 g (400 mmol) of carbazole [51555-21-6], 20.7 g (100 mmol) of 1, 3,5-tricyano-2,4,6-trifuorobenzene, 106.1 g

(500 mmol) of tripotassium phosphate (anhydrous) and 200 g of glass beads is stirred in 500 ml of dimethylacetamide at 160 ° C for 16 h. After cooling, 1000 ml of water are added, filtered off from the precipitated solid, washed twice with 300 ml of water, twice with 200 ml of methanol and then dried in vacuo. Further purification analogous to variant A.

Yield: 20.5 g (31.6 mmol) 31%. Purity: 99.9% n. HPLC.

Analogously, the following compounds can be represented:

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Example S64: 1,3,5-tris-cyano-2- (N-carbazolyl) -4,6-bis (N-3,6-diphenyl-carbazolyl) benzene, S64

A well-stirred suspension of 4.0 g (100 mmol) of sodium hydride, 60 wt .-% dispersion in mineral oil in 500 ml of THF is under ice cooling at about + 10 ° C in portions with 16.7 g (100 mmol) of carbazole [51555-21 -6] - Beware of hydrogen evolution! Foam! After completion of the addition, the mixture is 30 min. stirred and then portionwise with ice cooling so with 20.7 g (100 mmol) of 1,3,5-tncyano-2-fluoro-4,6-dichloro-benzene [25751-93-7] added that the temperature + 20 ° C not exceeds. After completion of the addition, the mixture is stirred for 2 h at + 10 ° C, then removed the cooling bath, allowed to warm to 20 - 25 ° C, stirred for 2 h and then heated for 6 h at 40 ° C. After cooling to

Room temperature is added 12.0 g (300 mmol) of sodium hydride, 60 wt .-% dispersion in mineral oil, the reaction mixture is cooled to + 10 ° C, and then added in portions with 95.8 g (300 mmol) of 3,6-diphenylcarbazot [56525 -79-2] - Beware of hydrogen evolution!

Foam! After completion of the addition, the mixture is stirred for 2 h at + 10 ° C, then removed the cold bath, allowed to warm to 20 - 25 ° C, stirred for 2 h and then heated for 16 h at 60 ° C. After cooling to

Room temperature, the reaction is terminated by dropwise addition of 30 ml of MeOH and then the reaction mixture is concentrated in vacuo almost to dryness. The residue is stirred hot twice with 600 ml of a mixture of 400 ml of methanol and 200 ml of water and then once with 500 ml of methanol. The cleaning is done by three times Recrystallization from dioxane (ca. 3.5 ml / g) followed by five recrystallizations from DMF (about 2 mL / g) twice, and fractional sublimation (p about 1 x 10 ^"5 mbar, T ca. 330-340 ° C) yield. : 22.9 g (24.0 mmol) 24% Purity: 99.9% n. HPLC.

Analogously, the following compounds are shown:

S71 20%

56525-79-2

17966-00-6

II) Synthesis of Precursors

Example S72-V: 9- (2,6-dibromo-phenyl) -9H-carbazole

A well-stirred suspension of 66.9 g (400 mmol) of carbazole [51555-21-6], 25.4 g (100 mmol) of 1,3-dibromo-2-fluorobenzene [363897-9], 106.1 g (500 mmol) of tripotassium phosphate (anhydrous ) and 200 g of glass beads are stirred in 500 ml Dimethyiacetamid 16 h at 160 ° C. After cooling, 1000 ml of water are added, filtered off from the precipitated solid, washed twice with 300 ml of water, twice with 200 ml of methanol and then dried in vacuo. After a single recrystallization

Toluene / heptane are obtained 18.9 g (47.2 mmol, 47%) and

then further implemented.

Analog implemented:

Example S74-V: 9- [2-Bromo-6- (4,4,5,5-tetramethyl- [1,3,2] dioxaborolan-yl) -phenyl] -9H-carbazole

18.5 (46.1 mmol, 1 eq) S72-V is taken together with 14.1 g (55.3 mmol,

1.2 eq) bis (pinacolato) diborane (CAS 73183-34-3) and 15.8 g (161 mmol, 3.5 eq) potassium acetate (CAS 127-08-2) in 100 ml THF and after degassing with 2.26 g (0.06 eq) 1,1-bis (diphenylphosphino) ferrocene-dichloropalladium (II) complex with DCM (CAS 95464-05-4). The batch is heated at reflux for 14 h and after the reaction has ended, water is added. The organic phase is separated and the aqueous phase extracted several times with dichloromethane. The combined organic phases are dried over sodium sulfate and the solvent removed in vacuo. There are obtained 15.3 g (34.1 mmol, 74%) of the product S74-V. Analog implemented:

Example S76-V: 9- [2-Bromo-6- (4,6-diphenyl, 3,5] triazin-2-yl) -pheny IJ-9H-carbazole S76-V

option A

15.0 g (33.5 mmol) of S74-V, 1.6 g (43.5 mmol, 1.3 eq of 2-chloro-4,6-diphenyl-1,3,5-triazine (CAS 3842-55-5) and 5.3 g of sodium carbonate are added to 200 1 ml of dioxane, 200 ml of toluene and 100 ml of water are added to this suspension 1.94 g (1.68 mmol, 0.05 eq.) of Pd (PPh ₃ ) _4. The reaction mixture is refluxed overnight and, after cooling, the precipitated solid is filtered off with suction, The residue is extracted with hot toluene and recrystallized from toluene / heptane to give 7.23 g (13.1 mmol, 39%) of product S76-V. Analog implemented:

III) Synthesis of Inventive Compounds and Precursors Example S78: 9- [3- (4,6-Diphenyl-1- [1,3,5] triazin-2-yl) -biphenyl-2-yl] -9H-carbazole

7.1 g (12.8 mmol) of S76-V, 1.72 g (14.1 mmol, 1.1 eq) of phenylboronic acid (CAS 98-80-6) and 5.45 g (25.7 mmol, 2 eq) of tripotassium phosphate are dissolved in 100 ml of dioxane, 100 ml of toluene and 50 Dissolved ml of water and degassed for 30 minutes. Subsequently, 86 mg (0.38 mmol, 0.03 eq.)

Palladium (II) acetate and 230 mg (0.77 mmol, 0.06eq.) Added tri-o-tolylphosphine and the mixture heated to reflux. After completion of the reaction the mixture is cooled, the aqueous phase separated and extracted several times with toluene. The combined organic phases are washed with water, dried over sodium sulfate and the solvent removed in vacuo. The residue is extracted with hot toluene and recrystallized from toluene / heptane. After sublimation, 4.1 g (7.4 mmol, 58%) of the desired product S78 are obtained with an HPLC purity> 99.9%.

IV) Synthesis of Precursors:

Example S81-V: ^ -Bromo ^ SAS ^ -pentafluoro-S '^' - bis-trifluoromethyl-biphenyl

A solution of 11.4 g (30 mmol) of 2,3,4,5,6-pentafluoro-3 ', 5 ^, -bis- trifluoromethyl-biphenyl [1363958-46-6] in 300 ml of dichloromethane is added dropwise with exclusion of light a mixture of 1.7 ml (32 mmol) of bromine and 20 ml of chloroform. After stirring at 40 ° C. for 16 h, 200 ml of ethanol and then 50 ml of saturated sodium sulfite solution are added. The colorless solid is filtered off, washed three times with 200 ml of water and three times with 100 ml of ethanol, dried in vacuo and then separated from isomers by recrystallization in DMF and toluene. Yield: 4.1 g (9 mmol), 30% of theory. Th.

Analogously, the following compounds can be obtained:

V) Synthesis of compounds according to the invention:

Example S91: 9- (2,6-Dimethylhenylene) -9H- [3,91bicarbazolyl

12.6 g (38.32 mmol) of 9H- [3.9 '] bicarbazolyl [18628-07-4], 7 g (38.32 mmol) of 2-bromo-1,3-ditrifluoromethylbenzene [118527-30 -3] and 16 g K ₂ C0 ₃ are suspended in 300 mL p-xylene. 0.86 g (3.84 mmol) of Pd (OAc) ₂ and 7.6 ml of a 1M tri-tert-butylphosphine solution are added to this suspension. The reaction mixture is refluxed for 16 h. After cooling, the organic phase is separated off, washed three times with 200 ml of water and then concentrated to dryness. The residue is extracted with hot toluene, recrystallized from toluene and finally sublimed under high vacuum. Yield: 14.5 g (35 mmol), 87% of theory. Th .; Purity 99.9%.

Analogously, the following compounds can be obtained:

VI) Synthesis of Precursors:

Example S106-V: a'.S '^', S'.e'-pentafluoro-a-trifluoromethyl-biphenyl-Z-ylamine

294 ml of concentrated hydrochloric acid, 700 ml of ethanol and 38 g (126 mmol) of 2,3 _> 4,5,6-pentafluoro-2'-nitro-3 ^* -trifluoromethyl-biphenyl [1261680-28-7] are initially charged at room temperature in portions with 35 g

(294 mmol) tin powder. After the addition, the mixture is stirred for 3 h at room temperature. Thereafter, the reaction mixture is adjusted to pH = 12 with ice-cooling by addition of NaOH (solid). The residue is filtered off, washed with dichloromethane and from heptane recrystallized. 22 g (79 mmol) of a white solid are obtained, corresponding to 63% of theory. Th.

Analogously, the following compounds with 2 eq. Tin powder can be obtained:

VII) Synthesis of compounds of the invention:

Example S109: 9- ^(3,2, ^3, ^_4,> ^5, ^6, -Hexafluoro-biphenyl-2-yl) -9H-carbazol

15.6 g (50 mmol) of 2,2'-dibromo-biphenyl are mixed with 500 ml of toluene, 2.3 g (2.5 mmol) of tris (dibenzylideneacetone) dipalladium (0), 10 ml of 1M t-Bu ₃ P in Toluene and sodium tert-butoxide added 11, 5 g (120 mmol). Subsequently, 11.8 g (40 mmol) of 2, 3 ^, 4 ^, 5, 6'-pentafluoro-3-trifluoromethyl-biphenyl-2-ylamine are added. The batch is heated at 110 ° C. for 20 h, then cooled to room temperature and 400 ml of water are added. give. It is extracted with ethyl acetate, then the combined organic phases are dried over sodium sulfate, and concentrated under reduced pressure. The residue is recrystallised from toluene and from dichloromethane isopropanol and finally sublimed under high vacuum. The purity is 99.9%. The yield is 10 g (23 mmol), corresponding to 59% of theory.

Analogously, the following compounds can be obtained:

B) Device examples

In the following examples, the results of various OLEDs are presented in which the compounds of the invention as

emitting compounds are used.

Glass plates coated with structured ITO (indium tin oxide) form the substrates for the OLEDs. The substrates are wet-cleaned (dishwasher, Merck Extran cleaner), then baked for 15 minutes at 250 ° C and before the coating with a

Treated oxygen plasma.

All materials are thermally evaporated in a vacuum chamber. The emission layer always consists of a matrix material and the emitting material. This gets through the matrix material

Cover vaporization mixed in a certain volume fraction.

The OLEDs are characterized by default. The

Electroluminescence spectra are determined at a luminance of 1000 cd / m ² and from this the CIE 1931 x and y color coordinates are calculated. Furthermore, the voltage required for a luminance of 1000 cd / m ² is determined. In Table 1 is still the external

Quantum efficiency indicated at an operating luminance of

1000 cd / m ^{2 is} achieved. This is determined assuming a Lambertian radiation characteristic.

Type 1

substrate:

ITO, 50nm Hole injection layer / hole transport layer:

4,4-bis [N- (1-naphthyl) -N-phenylamino] -biphenyl, cc-NPD, [123847-85-8], 90 nm emission layer:

4,4'-bis (N-carbazole) biphenyl CBP, [58328-31-7], doped as matrix material with 5% by volume of the compound according to the invention (see Table 1 as

Dotand, 15 nm electron transport layer:

1, 3,5-tri (1-phenyl-1H-benzimidazol-2-yl) benzene TPBi, [192198-85-9], 50 nm

Electron injection layer:

LiF, 1 nm

Cathode:

AI, 100 nm Typla

Same construction as Type 1, except that a layer 120 instead of 90 nm oc-NPD and a 60 instead of 50 nm thick layer TPBI is used. type2

substrate:

ITO, 50nm

Hole injection layer / hole transport layer:

4,4-bis [N- (1-naphthyl) -N-phenylamino] biphenyl, a-NPD, [123847-85-8], 80 nm

Hole transport layer:

1, 3-bis (9-carbazolyl) benzene, mCP, [550378-78-4], 10 nm Emission layer:

2,8-bis (diphenylphosphoiyl) dibenzo [b, d] thiophene, PPT, [1019842-99-9], doped as matrix material with 5% by volume of the compound according to the invention (see Table 1) as dopant, 20 nm electron transport layer:

2,8-bis (diphenylphosphoryl) dibenzo [b, d] thiophene, PPT, [1019842-99-9], 50 nm

Electron injection layer:

LiF, 1 nm

Cathode:

Al, 100 nm Use of compounds according to the invention as emitter materials in OLEDs

The compounds of the invention can be used in particular as emitter materials in the emission layer of OLEDs. The measured values for power efficiency, voltage and

Color coordinates are summarized in Table 1.

Table 1:

Emitter Type EQE (%) Voltage (V) CIE x y

Ex.

1000 cd / m ² 1000 cd / m ² 1000 cd / m ²

P1 S1 2 14.0 7.3 0.42 / 0.56

P2 S6 1 12.8 7.1 0.45 / 0.55

P3 S23 1 12.1 5.7 0.41 / 0.57

P4 S32 1 13.0 6.3 0.36 / 0.59

P5 S36 2 14.4 7.7 0.40 / 0.57

P6 S47 2 15.5 8.3 0.14 / 0.19

P7 S49 1 18.5 5.8 0.23 / 0.54

P8 S52 2 16.8 6.6 0.15 / 0.28

P9 S54 1 17.2 4.7 0.22 / 0.52

P10 S61 2 13.8 7.6 0.15 / 0.27

P11 S64 1a 13.8 6.3 0.59 / 0.41 P-V1 Comp.1 2 1.8 4.6 0.14 / 0.06

P-V2 Compare 2 1 1.3 3.7 0.69 / 0.31

The produced OLEDs show excellent values for the

Power efficiency. It is possible to obtain light with different color coordinates by using different emitters. Comparison with prior art compounds (Comp. 1 and Comp. 2 in P-V1 and P-V2) shows a superior improvement in power efficiency at similar voltages by replacing these compounds with the compounds of the present invention.

Compounds of Comparative Examples P-1 and P-V2:

Cf. Fig. 2

Claims

claims

1. Compound of formula (I)

Formula (I) or a compound containing exactly two or three units according to the formula (I), which are linked together via a single bond or a group L, where:

L is any divalent or trivalent organic

Group;

A is a group of the formula (A)

Formula (A),

which is bound via the dashed bond;

Ar ¹ is the same or different at each occurrence

aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may be substituted by one or more radicals R ¹ ; is the same or different at each occurrence

Single bond, BR ¹ , C (R ¹ ) _2l Si (R ¹ ) ₂ , NR ¹ , PR, P (= O) R ¹ , O, S, S = O or S (= O) ₂ ; is at each occurrence the same or different selected from a group of formula (A), H, D, a straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, each with one or a plurality of R may be substituted, wherein one or more CH ₂ groups in the abovementioned groups by -R ¹ C = CR ¹ -, -C = C-, Si (R ¹ ) ₂ , C = 0, C = NR \ -C (= O) O-, -C (= O) NR-, NR ¹ , P (= O) (R), -O-, -S-, SO or SO ₂ may be substituted, and an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, each of which may be substituted by one or more R ¹ radicals; is the same or different at each instance F, CF ₃ , C (= O) R ¹ , CN, P (= O) (R ¹ ) ₂ , S (= O) R ¹ , S (= O) ₂ R ¹ , a straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, each of which may be substituted by one or more radicals R ¹ , and wherein one or more CH ₂ groups in the abovementioned Groups represented by -R ¹ C = CR ¹ -, -C = C-, Si (R ¹ ) ₂ , C = O, C = NR ¹ , -C (= O) O-, -C (= O) NR ¹ -, NR ¹ ,

P (= O) (R ¹ ), -O-, -S-, SO or SO ₂ may be replaced, or an aromatic ring system having 6 to 30 aromatic ring atoms, which may be substituted by one or more radicals R, or a heteroaromatic ring system having from 5 to 30 aromatic ring atoms which is not bonded via a ring nitrogen atom and which may be substituted by one or more radicals R ¹ , where radicals R ^A may be linked to radicals R and form a ring; R ^B is selected from H, D and those listed above for R ^A

Radicals, where radicals R ^B can be linked to radicals R and form a ring;

R ¹ is the same or different H, D, F at each occurrence

C (= 0) R ^2, CN, Si (R ²⁾ ₃₎ N (R ²⁾ _2, P (= 0) (R ²⁾ _2, OR ^2, S (= O) R ^2, S (= 0 ) ₂ R ² , a straight-chain alkyl or alkoxy group having 1 to 20 C atoms or a branched or cyclic alkyl or alkoxy group having 3 to 20 C atoms, wherein the abovementioned groups are each substituted by one or more radicals R ² and wherein one or more CH ₂ groups in the abovementioned groups can be replaced by - R ² C =CR ² -, -C =C-, Si (R ² ) ₂ , C =O, C =NR ² , -C ( = 0) O-,

-C (= O) NR ² -, NR ² , P (= O) (R ² ), -O-, -S-, SO or SO ₂ may be replaced, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic Ring atoms, which may be substituted by one or more radicals R ² , where two or more radicals R ^{1 may} be linked together and form a ring; R ² is the same or different at each occurrence, H, D, F or an aliphatic, aromatic or heteroaromatic organic radical having 1 to 20 carbon atoms, in which also one or more H atoms may be replaced by D or F; two or more substituents R ^{2 may} be linked together and form a ring; with the proviso that at least one R ^{A is} selected from F, CF ₃ , CF ₂ H, CFH ₂ , C (= O) R \ CN, P (= O) (R ¹ ) ₂ , S (= O) R ¹ , S (= O) ₂ R ¹ or a group E, which is an aryl or heteroaryl group having 6 to 18 aromatic ring atoms, with one or more radicals

R ¹ may be substituted, and which contains as constituents of the aromatic ring one or more groups V, wherein the groups V are each the same or different selected from each = N-, = C (F) -, = C (CN) - and = C (CF ₃ ) -. A compound according to claim 1, characterized in that the group L is a divalent group selected from alkyl groups having 1 to 20 carbon atoms, in which one or more CH ₂ groups by Si (R ¹ ) ₂ , 0, S, C = 0, C = NR ¹ , C = 0-0, C = O-NR, NR ¹ , P (= O) (R), SO or SO ₂ may be substituted and substituted with one or more R ¹ may be, or aromatic or heteroaromatic ring systems having 5 to 30 aromatic ring atoms, each of which may be substituted by one or more radicals R ¹ , or a trivalent group selected from aromatic or heteroaromatic ring systems having 5 to 30 aromatic ring atoms, each by a or more radicals R ¹ may be substituted.

A compound according to claim 1 or 2, characterized in that Ar ^{1 is} identical or different at each instance and is an aromatic ring system having 6 to 20 aromatic ring streams which may be substituted by one or more R ¹ groups.

4. A compound according to one or more of claims 1 to 3,

characterized in that the group Y is, identically or differently, a single bond, C (R ¹ ) ₂ , NR ¹ , O or S at each occurrence.

Compound according to one or more of claims 1 to 4, characterized in that the group B in each occurrence is the same or different selected from a group of formula (A), H, a straight-chain alkyl group having 1 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms, each of which may be substituted with one or more R groups, and an aryl group having 6 to 14 aromatic ring atoms, each of which may be substituted with one or more R ¹ groups. Compound according to one or more of claims 1 to 5, characterized in that the group B is identical or different at each occurrence of a group of formula (A) or H.

Compound according to one or more of Claims 1 to 6, characterized in that the group B is a group of the formula (A).

A compound according to one or more of claims 1 to 7, characterized in that both radicals R ^{A are the} same or

are variously selected from F, CF ₃ , CN, or a group E, which is an aryl or heteroaryl group having 6 to 14 aromatic

Ring atoms which may be substituted by one or more radicals R ¹ and which contains as constituents of the aromatic ring one or more groups V, the groups V in each

Occurs identically or differently selected from = N-, = C (F) -, = C (CN) - and = C (CF ₃ ) -, and wherein the heteroaryl group is not bound via a nitrogen atom.

Compound according to one or more of claims 1 to 8, characterized in that R ^{B is the} same or different selected on each occurrence of H, F, CF ₃ , CN, a straight-chain alkyl group having 1 to 10 carbon atoms or a branched or cyclic Alkyl group having 3 to 10 carbon atoms, each of which may be substituted by one or more radicals R ¹ , and an aryl or heteroaryl group having 6 to 14 aromatic ring atoms which may be substituted by one or more radicals R ¹ , wherein the heteroaryl group is not bound by a nitrogen atom. Compound according to one or more of Claims 1 to 9, characterized in that the compound of the formula (I) corresponds to one of the formulas (1-1) to (I-3)

Formula (1-1) Formula (I-2) Formula (I-3), wherein to the free positions on the benzene ring in formula (I-2) optionally H, D, alkyl groups having 1 to 10 carbon atoms or

aromatic or heteroaromatic ring systems may be bonded with 6 to 30 aromatic ring atoms, each of which may be substituted by one or more radicals R ¹ , and wherein the groups A, R ^A and R ^{B are} as defined in one or more of claims 1 to 9 and the proviso is that at least one R ^{A is} selected from F, CF ₃ , C (= ^O ) R ¹ , CN, P (= O) (R ¹ ) ₂ , S (= 0) R ¹ , S (= O) ₂ R ¹ or a group E which is an aryl or heteroaryl group having 6 to 18 aromatic ring atoms which may be substituted by one or more radicals R ¹ and which contains, as constituents of the aromatic ring, one or more groups V contains, where the groups V at each

Occurrences are selected the same or different from = N-, = C (F) -, = C (CN) - and = C (CF ₃ H

Process for the preparation of a compound according to formula (I) according to one or more of claims 1 to 10, characterized

characterized in that at least one carbazole derivative by nucleophilic aromatic substitution or Buchwald coupling is introduced, or that at least one electron-poor

Heteroaryl group is introduced by Suzuki coupling.

12. Oligomers containing one or more compounds according to

Formula (I) according to one or more of claims 1 to 10, wherein the bond (s) to the oligomer can be located at any positions substituted by R or R ² in formula (I).

13. Electronic device comprising at least one compound according to one or more of claims 1 to 10, or at least one oligomer according to claim 12.

14. Organic electroluminescent device containing anode,

Cathode and at least one emitting layer, characterized in that at least one organic layer in the device, selected from emitting layers, at least one compound according to one or more of claims 1 to 10 or at least one oligomer according to claim 12 contains.

15. Use of a compound according to one or more of

Claims 1 to 10, or an oligomer according to claim 12, in an electronic device.